Electrolyte materials for solid oxide electrolyzer cells

ABSTRACT

A solid oxide electrolyzer electrolyte composition includes a scandia and ceria stabilized zirconia, containing 5 to 12 mol % scandia, 1 to 7 mol % ceria, and 80 to 94 mol % zirconia, or a yttria and ceria stabilized zirconia containing 3 to 10 mol % yttria, 1 to 6 mol % ceria, and 84 to 96 mol % zirconia.

FIELD

The present invention is directed to electrolyte materials for use in solid oxide electrolyzer cells (SOEC) that mitigate cathode delamination.

BACKGROUND

Solid oxide fuel cells (SOFC) can be operated as electrolyzer cells in order to produce hydrogen and oxygen from water. Such cells are referred to as solid oxide electrolyzer cells (SOEC). In SOFC mode, oxygen ions are transported from the cathode side (air) to the anode side (fuel) and the driving force is the chemical gradient of partial pressure of oxygen across the electrolyte. In SOEC mode, a positive potential is applied to the air side of the cell and the oxygen ions are transported from the fuel side to the air side. Since the cathode and anode are reversed between SOFC and SOEC (i.e. SOFC cathode is SOEC anode, and SOFC anode is SOEC cathode), the SOFC cathode (SOEC anode) is referred to as the air electrode, and the SOFC anode (SOEC cathode) is referred to as the fuel electrode. A SOEC includes a ceramic (e.g., solid oxide) electrolyte, an air electrode, and a fuel electrode. During SOEC mode, water in the fuel stream is reduced (H₂O+2e→O⁻²+H₂) to form H₂ gas and O⁻² ions, O⁻² ions are transported through the solid electrolyte, and then oxidized on the air side (2O⁻²→O₂) to produce molecular oxygen. Since the open circuit voltage for a SOFC operating with air and wet fuel (hydrogen, reformed natural gas) is on the order of 0.9 to 1V (depending on water content), the positive voltage applied to the air side electrode in SOEC mode raises the cell voltage up to typical operating voltages of 1.1 to 1.3V. In constant current mode, the cell voltages will increase with time if there is degradation of the cell which can arise from both ohmic sources and electrode polarization.

One of the major hurdles encountered with state-of-the-art SOEC is the delamination of the air electrode at high current densities. The degree of delamination increases with the current density and the flux of oxide ion transport.

SUMMARY

In one embodiment, a solid oxide electrolyzer cell electrolyte composition includes a scandia and ceria stabilized zirconia, comprising 5 to 12 mol % scandia, 1 to 7 mol % ceria, and 80 to 94 mol % zirconia. In one embodiment, the electrolyte composition comprises 5 to 10 mol % scandia, 1 to 5 mol % ceria, and 84 to 94 mol % zirconia. In another embodiment, the electrolyte composition comprises 5 to 10 mol % scandia, 2 to 5 mol % ceria, and 84 to 94 mol % zirconia. In one embodiment, the electrolyte composition further comprises 0.5 to 3 mol % ytterbia.

In another embodiment, a solid oxide electrolyzer cell electrolyte composition includes a yttria and ceria stabilized zirconia, comprising 3 to 10 mol % yttria, 1 to 6 mol % ceria, and 84 to 95 mol % zirconia.

A solid oxide electrolyzer cell includes the above electrolyte composition(s), an air electrode, and a fuel electrode.

FIGURES

FIG. 1A is a perspective view of a solid oxide electrolyzer cell (SOEC) stack, and FIG. 1B is a side cross-sectional view of a portion of the stack of FIG. 1A.

FIG. 2 is a plot of voltage at different current for different electrolyzer cells. The figure shows cell voltage of two electrolyte compositions (A and B) operated for extended periods of time at various currents.

DETAILED DESCRIPTION

FIG. 1A is a perspective view of a solid oxide electrolyzer cell (SOEC) stack 20, and FIG. 1B is a side cross-sectional view of a portion of the stack 20 of FIG. 1A. Referring to FIGS. 1A and 1B, the stack 20 includes multiple electrolyzer cells 1 that are separated by interconnects 9, which may also be referred to as gas flow separator plates or bipolar plates. Each electrolyzer cell 1 includes an air electrode 3, a solid oxide electrolyte 5, and a fuel electrode 7. The stack 20 also includes internal fuel riser channels 22.

Each interconnect 9 electrically connects adjacent electrolyzer cells 1 in the stack 20. In particular, an interconnect 9 may electrically connect the fuel electrode 7 of one electrolyzer cell 1 to the air electrode 3 of an adjacent electrolyzer cell 1. FIG. 1B shows that the lower electrolyzer cell 1 is located between two interconnects 9.

Each interconnect 9 includes ribs 10 that at least partially define fuel channels 8 and air channels 8 on opposite sides of the interconnect The interconnect 9 may operate as a gas-fuel separator that separates a fuel, such as a water vapor, flowing to the fuel electrode 7 of one cell 1 in the stack 20 from oxidant, such as air, flowing to the air electrode 3 of an adjacent cell 1 in the stack 20. At either end of the stack 20, there may be an air end plate or fuel end plate (not shown) for providing air or fuel, respectively, to the end electrode. The end plates are electrically connected to a power source (e.g., voltage or current source) which provides electrical power to the stack 20 for the electrolysis reaction in which water provided to the fuel electrode 7 is separated into hydrogen on the fuel side and oxygen which are transported from the fuel electrode 7 to the air electrode 3 through the electrolyte 5.

The air electrode 3 may comprise a mixture of an electrically conductive material and an electrically insulating ceramic material. The electrically conductive material may comprise a perovskite electrically conductive material, such as lanthanum strontium manganate, or a metal, such as platinum. The electrically insulating ceramic material may comprise an ionically conductive stabilized or partially stabilized zirconia (ZrO₂) material, such as a rare earth stabilized (e.g., doped) zirconia, such as scandia (Sc₂O₃) stabilized zirconia (SSZ), yttria (Y₂O₃) stabilized zirconia (YSZ), and/or ytterbia (Yb₂O₃) stabilized zirconia (YbSZ). The fuel electrode 7 may comprise a cermet material, such as a nickel and a stabilized zirconia and/or doped ceria cermet.

Without wishing to be bound by a particular theory, the delamination of the air electrode 3 may be caused by the precipitation of oxygen at the electrolyte/air electrode interface which can lead to high pressures resulting in air electrode delamination.

Embodiments of the invention provide electrolyte 5 materials that help mitigate the air electrode delamination and allow SOEC to operate at higher current densities. It has been found that increasing the amount of ceria in a Scandia-Ceria doped Zirconia fluorite material helps mitigate air electrode delamination. For example, SOEC's were tested with two different electrolyte materials with one having approximately twice the amount of ceria as the other. The electrolytes were A) 88 mol % ZrO₂-10 mol % Sc₂O₃-2 mol % CeO₂, which can written as Zr_(0.8)Sc_(0.182)Ce_(0.018)O_(2-x), and B) 88 mol % ZrO₂-10 mol % Sc₂O₃-1 mol % CeO₂-1 mol % Yb₂O₃, which can be written as Zr_(0.793)Sc_(0.180)Ce_(0.009)Yb_(0.018)O_(2-x). The SOEC stack consisted of cells numbered 1-5 with electrolyte A and cells numbered 6-10 with electrolyte B, and was operated for extended periods of time at the different currents, 1 A, 2 A, 4 A, 10 A, 15 A, and 20 A. At low currents (1-4 A), cells with both electrolyte compositions behaved well and similarly, as shown in the FIG. 2.

However, at higher currents (10A and above), the cells with electrolyte composition B (lower ceria content) exhibited a higher voltage increase during operation, indicating higher resistance and cell over potential. The two type of cells have the same air and fuel electrodes and the only difference is the electrolyte composition. Without wishing to be bound by a particular theory, the inventor believes that the higher ceria content in the electrolyte increases the electronic conductivity in the electrolyte, which mitigates the precipitation of oxygen at the electrolyte/cathode interface.

Based on these results, the following compositions of doped zirconia are provided for SOEC electrolyte 5 materials.

10 mol % scandia doped zirconia with 1 to 5 mol % CeO₂ doping as shown below:

-   -   89 mol % ZrO₂-10 mol % Sc₂O₃₋₁ mol % CeO₂;     -   88 mol % ZrO₂-10 mol % Sc₂O₃₋₂ mol % CeO₂;     -   87 mol % ZrO₂-10 mol % Sc₂O₃₋₃ mol % CeO₂;     -   86 mol % ZrO₂-10 mol % Sc₂O₃₋₄ mol % CeO₂;     -   85 mol % ZrO₂-10 mol % Sc₂O₃₋₅ mol % CeO₂.

9 mol % scandia doped zirconia with 1-5 mol % CeO₂ doping, as shown below:

-   -   90 mol % ZrO₂-9 mol % Sc₂O₃-1 mol % CeO₂ to 86 mol % ZrO₂-9 mol         % Sc₂O₃-5 mol % CeO₂;     -   8 mol % Scandia doped zirconia with 1-5 mol % CeO₂ doping;     -   7 mol % Scandia doped zirconia with 1-5 mol % CeO₂ doping;     -   6 mol % Scandia doped zirconia with 1-5 mol % CeO₂ doping;     -   5 mol % Scandia doped zirconia with 1-5 mol % CeO₂ doping.

Ytterbia may also be added to the scandia and ceria stabilized zirconia at 0.5 to 3 mol %, such as 0.75 to 1.5 mol %, as shown below:

-   -   10 mol % Scandia-1 mol % Yb₂O₃ doped zirconia with 1-5 mol %         CeO₂ doping;     -   88 mol Zr₂O₂-10 mol % Sc₂O₃-1 mol % Yb₂O₃-1 mol % CeO₂;     -   87 mol Zr₂O₂-10 mol % Sc₂O₃-1 mol % Yb₂O₃₋₂ mol % CeO₂;     -   86 mol Zr₂O₂-10 mol % Sc₂O₃-1 mol % Yb₂O₃₋₃ mol % CeO₂;     -   85 mol Zr₂O₂-10 mol % Sc₂O₃-1 mol % Yb₂O₃₋₄ mol % CeO₂;     -   84 mol Zr₂O₂-10 mol % Sc₂O₃-1 mol % Yb₂O₃₋₅ mol % CeO₂.

As above: 5-9 mol % Scandia doped zirconia-1 mol % Yb₂O₃-(1-5 mol % CeO₂).

Thus, compositions with at least 2 mol % ceria, such as 2 to 7 mol %, including 2 to 5 mol % ceria, are preferred based on FIG. 2.

In another embodiment, the electrolyte compositions may comprise yttria and ceria stabilized zirconia. The compositions may comprise 3 to 10 mol % yttria, 1 to 6 mol % ceria, and 84 to 96 mol % zirconia.

In one embodiment, the electrolyte composition comprises 3 mol % yttria, 1 to 5 mol % ceria, (such as 1, 2, 3, 4 or 5 mol % ceria), and 92 to 96 mol % zirconia. In another embodiment, the electrolyte composition comprises 8 mol % yttria, 2 to 6 mol % ceria, (such as 2, 3, 4, 5 or 6 mol % ceria,) and 86 to 90 mol % zirconia. In another embodiment, the electrolyte composition comprises 10 mol % yttria, 1 to 4 mol % ceria, (such as 1, 2, 3 or 4 mol % ceria), and 86 to 89 mol % zirconia.

The yttria and ceria stabilized zirconia may be formed by mixing yttria stabilized zirconia powder and ceria powder followed by sintering the powder blends into the electrolyte composition. Alternatively, the yttria and ceria stabilized zirconia may be formed by mixing yttria powder, zirconia powder and ceria powder followed by sintering the synthesized powders into the electrolyte composition.

8YSZ (8 mol % yttria stabilized zirconia) and CeO₂ powder blends may be formed as follows: mix (100-x) mol % 8YSZ powder with x mol % CeO₂ powder, where x ranges from 2 to 6, as shown in the Table 1 below.

TABLE 18 8YSZ + 2CeO₂ 8YSZ + 3CeO₂ 8YSZ + 4CeO₂ 8YSZ + 5CeO₂ 8YSZ + 6CeO₂

8YSZ and CeO₂ synthesized powders may be formed as follows: mix 8 mol % (Y₂O₃) with x mol % (CeO₂) and (92-x) mol % (ZrO₂) powders, where x ranges from 2 to 5, as shown in the Table 2 below.

TABLE 2 8YSZ + 2 CeO₂: synthesize 8 mol %(Y₂O₃) + 2 mol %(CeO₂) + 90 mol %(ZrO₂) 8YSZ + 3 CeO₂: synthesize 8 mol %(Y₂O₃) + 3 mol %(CeO₂) + 89 mol %(ZrO₂) 8YSZ + 4 CeO₂: synthesize 8 mol %(Y₂O₃) + 4 mol %(CeO₂) + 88 mol %(ZrO₂) 8YSZ + 5 CeO₂: synthesize 8 mol %(Y₂O₃) + 5 mol %(CeO₂) + 87 mol %(ZrO₂)

3YSZ and CeO₂ powder blends may be formed as follows: mix (100-x) mol % 3YSZ powder with x mol % CeO₂ powder, where x ranges from 1 to 5.

3YSZ and CeO₂ synthesized powders may be formed as follows: mix 3 mol % (Y₂O₃) with x mol % (CeO₂) and (97-x) mol % (ZrO₂) powders, where x ranges from 1 to 5.

10YSZ and CeO₂ powder blends may be formed as follows: mix (100-x) mol % 10YSZ powder with x mol % CeO₂ powder, where x ranges from 1 to 4.

10YSZ and CeO₂ synthesized powders may be formed as follows: mix 10 mol % (Y₂O₃) with x mol % (CeO₂) and (90-x) mol % (ZrO₂) powders, where x ranges from 1 to 4.

The preceding description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. 

1. A solid oxide electrolyzer electrolyte composition comprising a scandia and ceria stabilized zirconia, comprising: 5 to 12 mol % scandia; 1 to 7 mol % ceria; and 80 to 94 mol % zirconia.
 2. The electrolyte composition of claim 1, comprising: 5 to 10 mol % scandia; 1 to 5 mol % ceria; and 84 to 94 mol % zirconia.
 3. The electrolyte composition of claim 1, comprising: 5 to 10 mol % scandia; 2 to 5 mol % ceria; and 84 to 94 mol % zirconia.
 4. The electrolyte composition of claims 1, 2 or 3, further comprising 0.5 to 3 mol % ytterbia.
 5. A solid oxide electrolyzer electrolyte composition comprising a yttria and ceria stabilized zirconia comprising: 3 to 10 mol % yttria; 1 to 6 mol % ceria; and 84 to 96 mol % zirconia.
 6. The electrolyte composition of claim 5, wherein the electrolyte composition comprises: 3 mol % yttria; 1 to 5 mol % ceria; and 92 to 96 mol % zirconia.
 7. The electrolyte composition of claim 5, wherein the electrolyte composition comprises: 8 mol % yttria; 2 to 6 mol % ceria; and 86 to 90 mol % zirconia.
 8. The electrolyte composition of claim 5, wherein the electrolyte composition comprises: 10 mol % yttria; 1 to 4 mol % ceria; and 86 to 89 mol % zirconia.
 9. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 1; an air electrode; and a fuel electrode.
 10. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 2; an air electrode; and a fuel electrode.
 11. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 3; an air electrode; and a fuel electrode.
 12. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 4; an air electrode; and a fuel electrode.
 13. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 5; an air electrode; and a fuel electrode.
 14. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 6; an air electrode; and a fuel electrode.
 15. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 7; an air electrode; and a fuel electrode.
 16. A solid oxide electrolyzer cell comprising: the electrolyte composition of claim 8; an air electrode; and a fuel electrode.
 17. A solid oxide electrolyzer stack, comprising: a plurality of solid oxide electrolyzer cells of claim 9; and a plurality of interconnects separating the plurality of solid oxide electrolyzer cells.
 18. A solid oxide electrolyzer stack, comprising: a plurality of solid oxide electrolyzer cells of claim 13; and a plurality of interconnects separating the plurality of solid oxide electrolyzer cells. 